Solubilized derivatives of rosins and process of solubilization



a United States Patent ,Ofifice 3,041,326 SGLUBHJZED DEREVATIVES F ROSINS AND PROCESS OF SULUBILIZATHUN Charles V. Wilson and Wiliiam .l. Knox, In, Rochester,

N.Y., assignors to Eastman Kodak-Company, Rochester, N.Y., .a corporation of New Hersey I No Drawing. Filed Aug. 9, 1956, Ser. No. 603,195

11 Claims. (Cl. 260-97) This invention relates to new compositions of matter obtained from commercial rosin and to the use of these products, more particularly, their use as detergents and as coating aids. i 1

Rosin is a relatively inexpensive, commercially available material widely used for various purposes, as such, and in several modifications, for example those produced by hydrogenation or dehydrogenation. Rosin acids are useful surface-active agents particularly in combination with fatty soaps to impart increased solubility and foaming power. However, rosin soaps tend to discolor on aging and, like the fatty acid soaps, they are not resistant to lime and acids.

In order to avoid discoloration, rosin is modified commercially by hydrogenation or dehydrogenation. The former process eliminates the double bonds, while the latter partially aromatizes the compounds. In either case, the resulting products are less susceptible to oxidative deterioration. These hydrogenated or dehydrogenated rosins are used to increase the efficiency of soaps both for laundry and toilet purposes.

These treatments, however, do not make the matelials lime resistant nor do they increase the solubility substantially. One of the components of rosin, laevopimaric acid is made more soluble by reacting with maleic anhydride and hydrolyzing the maleopimaric acid thus formed to the sodium salt. However, laevopimaric acid makes up only 10 to 15% of the resin, and it has been considered desirable to solubilize all the rosin acids in the mixture. We have found that the solubility of 'these complex molecules may be improved and that in several cases the products have a high degree of calcium tolerance.

' We have also found that many of these materials have detergent properties which permit their use as Wetting agents and coating aids.

There are many instances in industry where it is desirable to apply one or more relatively thin coatings or layers to various type bases. In the photographic industry particularly, products are prepared by applying relatively thin coatings to various types of bases such as film and paper bases. ing's'be'uniform and that the coated base be free of bare spots or other imperfections. It is also desirable to apply such coatings at good production speeds for eificiency of operation. v

:In the coating of photographic film or paper with a gelatin layer such as a photographic emulsion or other coating compositions, a uniform coating must be obtained. In the absence of a coating'aid, numerous small crs'ecent-shaped uncoated areas are observed in the final 1 product. These defects may be the size of a pin head with streaks running from the points of the crescent in a direction opposite to that of coating. Sometimes lightly coated areas from 5 to mm. in diameter may also appear.

7 Various surface-active agents have been employed in gelatin coating compositions for facilitating coatingprocedures or operations For, instance, saponin has :been used for this purpose and eliminates many of the defects in coatings, giving a uniformly even coating particularly where the gelatin layer is applied to a dry. surface.

It is usually preferable that these coat-' Patented'June 26, 1962 Saponin, however, is a naturally occurring material of vegetable origin and may vary markedly from batch to batch in quality as well as composition. The quality of some batches of saponin may cause an increase in fog or a decrease of sensitivity of certain emulsions or may even rseult in no improvement in the coating properties of the composition to which it is added. These wide variations in the quality of this natural material make preferable, as coating aids, surface-active agents which are reproducible frombatch to batch both in chemical composition and coating behavior.

A number of synthetic agents have utility for coating purposes, but they are often deficient in some respects.

other object of this invention is to provide highly Watersoluble rosin derivatives which have a high degree of calcium tolerance. An additional object is to provide a coating aid free from photographic activity for coating photographic emulsions. Another object is to provide a method for applying gelatin coatings in the preparation of photographic materials which are uniformly even and repellency free and which are photographically inert. A further object of our invention is to prepare Wetting agents which may be used as detergents. Other objects will appear herein.

We have found that ordinary rosin, laevopimaric acid, the mixture of rosin acids remaining after removal of the laevopirnaric acid, and related products will react'with isocyanato esters, particularly those derived from aspartic and glutamic acids. The resulting materials can be selectively hydrolyzed to the sodium salts of acids which are highly water soluble and have a high degree of calcium tolerance. The reaction with the abietic acid portion of the mixture (and the others react similarly) may be represented as follows:

H30 00 OH I OONCHCOOR (CH2)nCOOR mo CONHOHOOOR CH(GH )9 (CHg)nG O ONa H3O OONHCHCOONB.

OEXOHg);

CED-C ONE i i emons:

CH-COONa in R may be .H, CH3, C2H5, C5H5 or --(CH COONa Where 11:1 to 3. These products are hereinafter referred to as sodium salts of maleopirnaroyl-amino acids. Thus, for example, if R is CH the product is trisodium maleopimaroylglycinate, while if R is CH COONa, the product is tetrasodium maleopimaroylaspartate.

Other products derived from rosin, for example, Abitol and Rosin Amine D and various hydrogenated and dehydrogenated forms of the mixture of alcohols or amines, as well as their polyoxyethylene'derivatives also react with isocyanato esters to produce urethanes and ureas respectively.

Rosin Amine D is the trade name for a commercially available material which is essentially l-aminomethyl-7- isopropyl 1,4a dimethyl 1,2,3,4,4a,9,10,10a octahydrophenanthrene.

Abitol and the products derived from it by treatment with ethylene oxide are particularly useful because further treatment with any of a numberof isocyanato esters produces, after selective hydrolysis, products of high water solubility and a high degree of calcium tolerance. Substances of this type are available on the market under the trade names Synthetics AD-50, Synthetics AD- 150 and Synthetics A-D-400. Abitol comprises a mixture of the three alcohols having about 15% of nonalcoholic material and corresponding ratios of 45% tetrahydroabietyl alcohol, 15% dehydroabietyl alcohol, and 40% dehydroabietyl alcohol having the following structures:

The 15% comprising the average non-alcohol portion of Abitol contains approximately 3-8% ester which can be considered as methyl esters of hydrogenated rosin; the remainder about 742%, is similar to the hydrocarbon fractions occurring in hydrogenated rosin.

The derivatives of Abitorformed by treatment with ethylene oxide may be represented as a mixture of the following three structures:

C ICHa):

CH3 CHzO (CHrCHaOhH 0H3 cnrotornoaroina n may be l-lO but in our preferred embodiment, n is 3 to 6. Synthetics AD-5O represents a derivative of Abitol with ethylene oxide in which n is about 5.4.

The materials described in the following examples as sodium rosinyl glutamate and sodium rosinyl aspartate are amides which were obtained by reacting a mixture of rosin acids with dimethyl isocyanatoglutarate or succinate. The term rosinyl is used here to signify the 'acyl radicals of the mixture of rosin acids present in commercial rosin. Tetra-sodium maleopimaroylglutarnate and aspartate are also amides prepared by reacting maleopimaric acid with the appropriate isocyanato ester and selectively hydrolyzing the primarily formed amide-ester. The Rosin Amine D derivative referred to in Example 12 is a urea prepared by reacting Rosin Amine D with the isocyanato ester. The last three materials in Examples 13-16 are urethanes obtained by the reaction of the isosyanato ester with a rosin alcohol known as Abitol or polyethoxy derivative thereof.

The following examples illustrate our invention but are not to be construed as limiting it in any way.

EXAMPLE 1 Sodium Rosinylaspartate evolution of carbon dioxide during the first few hours of of alcohol and filtered. To the alcohol solution at 33 was added a solution of 15 parts of sodium hydroxide in 15 parts of water and 150 parts of alcohol. Precipitation of a solid began shortly after mixing, and the temperature rose to about 45. The solid tends to form a gum if heated above this temperature so the mixture was allowed to stand for several hours to insure complete hydrolysis of the ester groups. The resulting sodium salt was collected on a filter, washed with acetone, and dried. The yield was about 30 parts.

Removal of solvent from the filtrate, using benzene to 'azeotrope off the last of the water, left 52 parts of a darker solid than that described above. Both solids are very soluble in water, have a high calcium tolerance, and are active surface-active agents.

Since commercial rosin is a mixture of several related.

acids, the reaction is best represented as follows:

Rosin+ CNCHC 0 0 OQHE 0.111501 CHzC O 0 02115 A R0sinyl-CONHCHC O O CzHs ZNaOH CHiCOOC H Rosinyl-CONHCHCOONa CHzCGONa EXAMPLE 2 Tetrasodium Maleopz'm'aroylaspartate A solution of 40 grams (0.1 m.) of maleopirnanic acid (obtained from gum oleoresin by treatment with maleic anhydride as described in US Patent 2,359,980) and 21.5 g. (0.1 m.) of diethylisocyanato succinate in 60 ml. of chlorobenzene was heated for 16-18 hours at the boiling point. Carbon dioxide was evolved during the early stages of the reaction. The solvent was rem oved by heating on the steam bath under reduced pressure, and the residue was dissolved in 300 ml. of alcohol. Treatment of this solution with a solution of 16g. (0.4'm.) of sodium hydroxide in aqueous alcohol (made by dissolving a the sodiumhydroxide in 20 ml. of water and diluting with 200 ml. of alcohol) caused precipitation of a gummy solid. The mixture was heated for an hour at 65, allowed to come to room temperature, and the aqueous alcohol removed by decantation. Acetone was added and the solid ground to a powder by use of a mortar and pestle, or alternately, by vigorous stirring with a Lightnin mixer. The solid was collected on a filter, washed with acetone and dried. The yield of product was 55-60 g. It had high water solubility, excellent calcium tolerance, and good surface-active properties.

I A similar product, tetrasodium maleopimaroylglutamate, results by treatment of maleopimaric acid with dimethyl isocyanatoglutarate by the same procedure. Similar products may be obtained by using isocyanato esters such as those derived from glycine, a-alanine, leucine and the like. r

EXAMPLE 3 Urea From Rosin Amine D (Hercules) and Dimethyl Isocyanato Succinate Dimethyl isocyanato succinate (23.5 g.) was added to 36 g. (1 molar equivalent) of Rosin Amine D. There was considerable heat of reaction, the temperature rising to 70-80. The mixture was heated for several hours at On cooling it set to a resin-like mass. It was dissolved in alcohol and treated with g. of sodium hydroxide dissolved in 12 ml. of water, and diluted with alcohol. There Was a small temperature rise; hydrolysis was completed by heating for 1-2 hours at 65. The

sodium salt which separates in resinous form became solid on cooling. The aqueous alcohol was removed by decantation, and a mixture of acetone and ethyl acetate added. After standing overnight, the solid was broken up, collected on a filter, washed with acetone, dried,

powdered, slurried with acetone, refiltered, and dried. The product (52 g.) was soluble in water but not tolerant of calcium. It was essentially N-u,fi-dicarboxyethyl-N- (7 isopropyl-1,4a dimethyl)-1,2,3,4,4a,9,10,10a-octahydrophenanthrylmethylurea (disodium salt was dissolved in 1500 ml. of ethanol and treated while being stirred with g. of sodium hydroxide in ml.

r of water. After the addition of the alkali, the mixture was heated at 75 for an hour, cooled, and the solid col lected on a filter, Washed with alcohol, and dried. There was obtained about 750 g. of granular product which has The matecoating assistant.

EXAMPLE 5 7 N-Carbo Abz'tyl Oxypolyethoxyglycine (Na Salt) A mixture of 75 g. of Synthetics AD-50, a derivative of Abitol (see Example 4) with ethylene oxide, and 26 g. of ethyl isocyanatoacetate reacted exothermically.

When the primary reaction was over, the. mixture was heated at 70-80" for 5-6 hours, and the product dissolved in 300 ml. of alcohol. To the alcoholic solution was added 10 g. of sodium hydroxide in 12 m1. of water. The mixture was heated at 6570 for about one-half hour and then allowed to stand for several hours. A

small amount of solid that separated in the solution was' removed by filtration; it was the disubstituted urea formed from the ethyl isocyanatoacetate. The water and alcohol were removed from the filtrate under reduced pres sure to give 88 g. of a syrup which could be dissolved in water to give a solution of any desired strength. Alternately, the hydrolysis can he carried out with water and the aqueous solution thus formed adjusted to the desired strength, Sodium N-carboabityloxypolyethoxyglutamate can be prepared by a similar procedure.

Abitol is essentially a mixture of threealcohols of the following structures:

CH3 CHzOH HaC --CH(OH2)2 CH3 onion .l. TIL

The name given to the product of this example is chosen to indicate that said product is a mixture of theurethanes of these three alcohols.

Y EXAMPLE 6 In an air knife application to paper of a silver bromide emulsion involving the use of sodium rosinyl glutamate carboabityloxyglutamate (SCG), as a coating aid, the following results were obtained:

SRG as a coatin aid the followin results were Concentration Repellencies Photographic g g Coating Aid grams per per 7.5 it. sq. Properties 0 8.1116 pound Concentration, Repellencies Photographic o. 0 10 Satisfactory. Coating Aid grams per per 7.5 it. sq. Properties 0.13 10 D0. pound 0.25 2 Do. 0.5 0 D0. 1.0 0 Do. 0. 0 1 Satisfactory. as i s 0. 0.5 0 Do. EXAMPLE 12 1.0 2 Do.

In an experiment similar to that described in Example EXAMPLE 7 15 6, but involving sodium N-carboabityloxyglycinate (SAG) as a coating aid,the following results were ob- In an experiment similar to that described in Example mined; 6, but involving sodium rosinyl aspartate (SRA), the followin r sul were obtained:

g 6 ts 2O Concentration, Repellcncles Photographic Coating Aid grams per per 7.5 ft. sq. Properties Concentration, Repellencies Photographic pound Coating Aid grams per per 7.6 it. sq. Properties pmnd 0.0 o Satisfactory.

tr: 8 s- 0.0 3 Satisfactory. 0.13 0 Do. 0 3- 0. 1 D0. L0 3 0.5 0 Do. 1.0 2 Do.

EXAMPLE 13 EXAMPLE 8 In an experiment similar to that described in Example In an experiment similar to that described in Example 6, but involving tetra-sodium maleopimaroylglutamate (SMG) as a coating aid, the following results were obtained:

In an experiment similar to that described in Example 6, but involving tetra-sodium maleopimaroylaspartate (SMA) as a coating aid, the following results were obtained:

6, but involving a product as described in Example 5, sodium N-carboabityloxypolyethoxy glutamate (SCPG), the following results were obtained:

EXAMPLE 14 In an experimental pelloid coating obtained by using the slide hopper coating technique described in US. Patent No- 2,681,294 and involving the product of Example 4, sodium N-carboabityloxyglutamate (SCG), at 0.22

gm./lb. of coating melt as a coating aid, the following result wer Concentration, Repellencies Photographic s e Obtained Coating Aid grams per per 7.5 it. sq. Properties pound Repellen- Nature of eies, 25 ft. Mottle Stroakiness Dried 0. 0 3 Satisfactory. q Surface 0.13 0 Do. 0.25 0 D0. 0.5 0 Do, Blank 4 sl.tosl.+.. sl Rough, 1.0 0 Do, 80G 0 s1 sl Du.

EXAMPLE 10 XA 15 In an experiment similar to that described in Example 6, but involving the Rosin Amine D Derivative (RDA) as a coating aid, the following results were obtained:

' Concentration, Repellencies Photographic Coating Aid grams per per 7.5 It. sq. Properties pound 0. 0 3 Satisfactory. 0.13 3 Do. 0.25 1 D0. 0. 6 1 Do. 1. 0 1 Do.

EXAMPLE 1 1 In an experiment similar to that described in Example 6, but involving the product of Example 4, sodium N- In an experiment similar to that described in Example 14, but involving the product of Example 5, sodium N-carboabitylpolyethoxyglycinate (SAPG), as a coating aid, the following results were obtained:

9 sodium N-carboabityloxypolyethoxyglutamate (SCPG the following results were obtained:

In an X-ray emulsion coating trial in which a product as described in Example 5, sodium N-carboabityloxypolyethoxyglutamate was used, the ease of the wet-on-wet coating was essentially equivalent to that obtained with oleoylpolypeptide, an excellent wet-on-wet coating aid derived from hydrolyzed gelatin and oleoyl chloride, which is used as a standard of coating excellence. The photographic properties of this material are very satisfactory in many emulsion systems. The ratio by weight of coating aid to coating melt was .1 gram to 2.5 pounds in the emulsion and 0.1 gram to 7.7 pounds in the overcoat.

EXAMPLE 18 In runs similar to those in Example 17 but using the product of Example 5, sodium N-carboabityloxypolyethoxy glycinate, at concentrations of 1.0 gram to 2.5 pounds of wet emulsion and 1 gram to 7.7 pounds of overcoat melt, comparably good results Were obtained.

Examples 17 and 18 are wet-on-wet coating examples where a warm overcoat is applied to a wet emulsion surface which has been set by chilling.

The term rosiny has been applied to the 19 carbon alkylated hydrophenanthrene nucleus which occurs in the rosin acids and the partially hydrogenated rosin acids. Rosinyl is thus weil known as the generic name of the C H and C I-I radicals which occur in abietic acid, levopimaric acid, neoabietic acid, dextropimaric acid and like acids Whose general formula is C H COOH, and dihydroabietic acid, dihydrolevopimaric acid, dihydrodextropimaric acid and like acids whose general formula is C H COOH. The term rosinyl is likewise here applied broadly to the C I-I and the C H radicals which occur in the rosin acids and the dihydrorosin acids. The term hydrorosinyl refers tov the C H radical having the ring structure of the fully hydrogenated rosin acids, and the term dehydrorosinyl refers to the C H radical having the ring structure of dehydroabietic acid. The terms norabietyl, nordihydroabietyl, nortetrahydroabietyl, and nordehydroabietyl are the specific names applied to those radicals which have the ring structure of abietic acid, dihydroabietic acid, tetrahydroabietic acid and dehydroabietic' acid respectively wherein the point of linkage is carbon number one.

When the compositions disclosed herein are used as coating aids, the aid may be incorporated ina gelatin coating which is coated on various supports such as paper, film base, glass and the like. In addition, some of these materials may be used for coatings over wet surfaces as well as dry surfaces. For instance, they may be used as coating aids when a gelatin emulsion is coated over a previous gelatin emulsion which is still in a wet condition such as a wet chilled emulsion surface. Moreover, some of these coating aids may be used in a series of gelatin layers and the subsequent gelatin layer containing one of these coating aids may be coated over a wet chilled emulsion surface, in which wet chilled emulsion has been incorporataed one of these coating aids. Other combinations of layers in wet or dry condition and in various sequences in which one or more layers contain one of these coating aids are intended to be within the scope of our invention.

Water-soluble salts other than the sodium salts are also within the scope of this invention and may be formed by using the appropriate hydroxide such as potassium hydroxide, ammonium hydroxide and the like to hydrolyze the ester. These coating aids are also advantageous with a multiple layer coating technique of the type described in U.S. patent application Serial No. 489,863, now U.S. Patent No. 2,761,791. We claim:

1. A composition of matter having the following formula:

R(X)nooNHOHo00R" l in which R is the carbocyclic nucleus of a rosin acid selected from the class consisting of rosinyl, hydrorosinyl and dehydrorosinyl radicals, in which n is 0-1 and when n is 1, X is CH NH, R is selected from the class consistof alkyl radicals having 14 carbon atoms, hydrogen, phenyl, COGR", CH COOR", (CH COOR",- and (CH COOR", and R" is an alkyl group having 1-3 carbon atoms.

2. A composition of matter having the following formula:

r cn cn cooua, and (CH COONa.

3. A composition of matter having the following formula:

CHQC o ONa RooNH-oH-o OONa in which R is a rosinyl nucleus.

5 A composition of matter comprising a mixture of the following structures:

C H\ /CH2OC ONHCHC 0 ON!!- OHaCHaCOONa Cl\T /CH2O C ONHCHC O 0N8 CEaCHgC 0 ONE K QM 11 GEQ/GHQOCONHCECOONH CHaCHzCOONa CH(CH2)2 in which the structures are represented in the mixture in the amounts of 45%, 15%, and 40%.

6. A process of solubilizing a complex molecule by reacting an isocyanato ester having the following general formula:

CNCHC o o R in which R is an alkyl group having 1-3 carbon atoms and R is selected from the class consisting of H, phenyl, alkyl with 1-4 carbon atoms, COOR, CH COOR,

(CH COOR and (CH COOR in which R is an alkyl group having 1-3 carbon atoms, with a material selected from the class consisting of rosin, rosin acids, 1-amino-methy1-7-isopropyl 1,4a dimethyl 1,2,3,4,4a,9,10,10a octahydrophenanthrene, rosin alcohols, hydrogenated rosin acids and dehydrogenated rosin acids and hydrolyzing the ester linkage with alkali.

7. A process of improving the solubility of rosin acids comprising reacting a mixture consisting essentially of rosin acids with an isocyanato ester having the following general formula:

OONoHGOOR R! in which R is an alkyl group having 1-3 carbon atoms and R is selected from the class consisting of H, phenyl, alkyl with 1-4 carbon atoms, COOR, CH COOR,

(CH2) 2C0 OR (CH 2C0 OR and (CH COOR and hydrolyzing the ester linkage with alkali.

9. A process of improving the solubility of rosin alco- 12 hols comprising reacting a mixture consisting essentially of rosin alcohols withan isocyanato ester having the following general formula:

OCNoHGOOR in which R is an alkyl group having 1-3 carbon atoms, and R is selected from the class consisting of H, phenyl, alkyl with 1-4 carbon atoms, COOR, CH COOR, (CH COOR, and (CH COOR and hydrolyzing the ester linkage with alkali.

10. A process of improving the solubility of dehydrogenated rosin acids comprising reacting a mixture consisting essentially of dehydrogenated rosin acids with an isocyanato ester having the following general formula: OONKJHCOOR R! in which R is an alkyl group having 1-3 carbon atoms, and R is selected from the class consisting of H, phenyl, alkyl with 1-4 carbon atoms, COOR, CH COOR, (CH COOR, and (CHQ COOR and hydrolyzing the ester linkageswith alkali.

11. A process of improving the solubility of polyoxyethylene derivatives of rosin alcohols whichare formed by reacting rosin alcohols with ethylene oxide comprising reacting a mixture. consisting essentially of polyoxyethylene derivatives of rosin alcohols with an isocyanato ester having the following general formula:

OONCHCOOR in which R is an alkyl group having 1-3 carbon atoms, and R is selected from the class consisting of H, phenyl, alkyl with 1-4 carbon atoms, COOR, CH COOR, (CH COOR, and (CH COOR and hydrolyzing the ester linkage with alkali.

References Oited in the tile of this patent UNITED STATES PATENTS 2,035,024 Schur Mar. 24, 1936 2,354,662 Bryce Aug. 1, 1944 2,472,437 Pratt June 7, 1949 2,499,430 Vogel et a1 Mar. 7, 1950 2,750,365 Subluskey June 12, 1956 2,875,214 Humphlett et a1 Feb. 24, 1959 FOREIGN PATENTS 676,511 Germany June 8, 1939 1,037,362 France Sept. 16, 1953 OTHER REFERENCES Brewster: Organic Chemistry, page 228, Prentice-Hall (1948).

Pinner: Plastics, vol. l1,pages 2061l; 215; 257 (1947).

Stafi Report, Paint, Oil and Chemical Review, vol. 116, pages 28-30, No. 26 (1953). 

1. A COMPOSITION OF MATTER HAVING THE FOLLOWING FORMULA: 